Preparation of hydrocarbon sols



Patented Dec. 30, 1947' 2 a angst raaraaa'rrou or nrnaooaanon sons Morris D. Marshall, Arlington, Mass, assignor to Monsanto Chemical Company, St. Louis, Mo.. a corporation of Delaware No Drawing.

Original ap lication September 3, 1941, Serial No. 409.434, now Patent No. 2,386,247. dated October 9, 1945. Divided and this application August 28, 1945, Serial No.

This invention relates to the preparation'oi sols, and particularly to the preparation of substantially anhydrous and salt free organosols, such as sols containing hydrocarbons and the like as the continuous phase.

There are several known methods for making substantially anhydrous organosols. For example, it is old to add alcohol to aqueous silicic acid, and then to remove the water by such means as dialysis or exposure in a confined space to the drying action of dry carbonate of potash or quicklime, It is also old to add glycerine to a 2% colloidal silicic acid solution with heat and agitation, and then to evaporate the water to obtain a clear transparent, highly viscous mass of colloidal silicic acid in glycerine. However, the products prepared in the above manner are either of low concentration or of low stability and therefore are not suitable for many industrial purposes for which they might otherwise be adapted.

It is accordingly a primary object of this invention to prepare vary stable and highly dis-- persed inorganic oxide sols in substantially anhydrous organic solvents which are of unusually high concentrations, e. g. contain as much as twenty-five per cent oxide or more.

A further object of the invention is to prepare substantially anhydrous $015 of a relatively high degree of concentration and stability containing either aromatic or aliphatic hydrocarbons as the continuous phase.

A still further object of the invention is to prepare sols of the above nature which contain only a relatively small amount of inorganic salt.

Still further objects and advantages of the invention will appear from the following description and appended claims. Before explaining in detail the present invention, however, it is to be understood that the invention is not limited in its application to the details described herein,

since the invention is capable of other embodiments and of bein practiced'or carried out in various ways. Also it is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation, and it is not intended to limit the in- 2 Claims. (Cl. 252 309) plete removal of the water by distillation, thereafter removing the precipitated inorganic salt, as by filtration, centrifuging or the like, and finally removing the water by distillation.

The above process results in the production of organosols which are substantially free of water, i. e. contain not more than about 1% of water. Products containing only traces of water may, however, easily be obtained in accordance with the invention by subjecting the above sols to a second or third distillation, which may or may not involve replacement of the original organic solvent with another organic solvent. Although the organic solvent initially employed should be miscible with water, the solvent used to replace it may be either water-miscible. or water-immiscible.

The organic solvent initially employed should be of such a nature as to cause substantially complete precipitation of inorganic salts and should either have a boiling point higher than that of water, i. e. sufficiently higher to permit substantially complete removal of the water by simple distillation, or it should be capable of forming a constant boiling mixture with water, either by itself or in combination with a third or a plurality of additional components, which mixture can then be fractionally or otherwise distilled oil; leaving as the residue a $01 containing the desired organic liquid as the dispersing medium or continuous phase. A most suitable solvent for forming a binary C. B. M. (constant boiling mixture) with water is normal propyl alcohol, which not only is highly miscible with water, but is relatively cheap and may be readily obtained in large quantities.

The sols made by distilling constant boiling mixtures, such as those described above, cannot only be made in an unusually high state ofconcentration, but are substantially free of water.

Thus, they may be directly made with as little as 1% or less oi H20. Moreover, they may be readily processed, as by replacement, to produce sols having relatively high boiling water immiscible organic solvents as the continuous phase. For example, the propyl alcohol in the sols prepared as described above may be replaced with aliphatic and aromatic hydrocarbons and the like, by mixing the initial alcohol sol with one or more of the above solvents and distilling oil? the initial alcohol, either as such or in the form of a constant boiling mixture. The resulting sols have been found to contain even less water than the sols prepared directly from the constant boiling mixtures,

As suitable organic solvents or liquids for replacing the initial alcohol sols may be mentioned such substances as benzene, toluene, and aliphatic hydrocarbons, such as "lactol spirits.

Another method of further reducing the water content of sols formed from binary constant boiling mixtures, such as the propyl alcohol sol prepared as described above, involves forming a ternary constant boiling mixture by adding to the resulting 501 an organic solvent, such as benzene, dichloroethylene, and trichloroethylene and an additional quantity of the original organic solvent, and then fractionally distilling the resulting ternary mixture. The distillation product is an organosol containing only a trace of water. Thus, in the case of propyl alcohol it is possible d still off both binary and ternary constant boiling mixtures with the result that sols having this alcohol as the continuous phase may be readily made containing very minute amounts of water.

The sols prepared from ternary constant boiling mixtures and containing only a trace of water. such as the propyl alcohol and like sols prepared as described immediately above, may be readily converted to sols containing water-immiscible organic solvents as the continuous phase, For example, the propyl alcohol in such sols may be replaced by toluene or other hydrocarbons by merely mixing the hydrocarbon ,with the substantially water free alcohol sol and distilling the resulting mixture. Sols of this nature are ordinarily very diflicult to obtain, but may be readily pre ared in accordance with the above method.

The organic solvent or liquid employed should be added to the aquasol in sufllcient amounts not only to precipitate the inorganic salt contained therein, but to prevent gelation during the early stages of the distillation during which water is removed, and to permit substantial y com lete removal of the water.- This usually results in the formation of an intermediate organo-aquasol containing about 3% silica.

The aquasols treated or used in connection with the above processes may be prepared in various ways. In the case of silica sol, for example, they are preferably prepared by reacting an aqueous solution of sodium silicate with dilute sulfuric acid in suitable proportions. Anv other suitable method may however, be employed, depending upon the particular oxide sol which it is desired to prepare.

In general, it is preferable to use aouasols having a high concentration of the colloidal oxide in connection with the processes of this invention,

. as this permits the use of less organic solvent stantially anhydrous sols of high concentration Example I.'Ihree hundred fifty-eight pounds of sodium silicate containing 28.7% 8102, 8.9% NazO and 62.4% H2O are diluted with one hundred sixty-two pounds of water. This mixture is then added to one hundred sixty-three and one half pounds of 31% sulfuric acid and the mass is agitated to distribute the silicate throughout the acid. The mixing is carried out in a suitable acid resistant apparatus at a temperature of about 15 C., and results in a silica sol having a pH of about 2.5. One thousand three hundred and seventy-five pounds of normal propyl alcohol are then added to the sol gradually with stirring while maintaining the temperature at about 15 C. This causes precipitation of substantially all of the inorganic salt, which is then removed by filtering or centrifuging. To the clear sol one thousand five hundred and forty pounds of additional normal propyl alcohol are added, which reduces the S102 content to about 3%. The sol is then distilled in a lead still equipped with a stirrer and a fractionating column. During the distillation the refluxing ratio is maintained in such a manner as to obtain 73% propanol in the first 50% of the distillate, about 92% propanol in the next 20% of the distillate, and about 99% propanol in the last 30%, which leaves as a residue at sol containing about 25% Si02.

Example II.A mixture containing one part by weight of the 25% propyl alcohol sol prepared in accordance with Example II, two parts by weight of anhydrous normal propanol and one and one-quarter parts by weight of benzol is distilled in a distillation apparatus equipped with a stirrer and a fractionating column having 28 theoretical plates, which results first in the removal of the water layer which forms and then in the removal of the C. B. M. containing normal propanol and benzol. The distillation is continued until the final dehydrated sol, containing only a trace of water, has been concentrated to a 25% SiOz content.

Example III.Five parts by weight of toluene are added to one part by weight of the normal propanol sol containing 25% SiOz obtained in accordance with Example IV. The resulting mixture is then distilled in a distillation apparatus provided with a stirrer and a fractionating column until all the normal propyl alcohol is removed as a C. B. M. and the resulting toluene sol contains an SiOz content of about 15%.

As indicated by the above examples, the method of this invention not only permits the production of highly concentrated and stable organosols which are substantially free of water, but they render it possible to prepare substantially salt free sols having a wide variety of hydrocarbon solvents as the continuous phase, without resorting to cumbersome and time consuming methods of removing the salt, such as dialysis or the like. The organic solvents used or present in the final sol may be either high boiling or low boiling water-immiscible solvents. Moreover, they may comprise or consist of such hydrocarbons or mixtures of hydrocarbons. as benzene,

toluene, lactol spiritsor the like, which heretofore it has not been possible to successfully prepare as sols of the type described.

Although the above examples refer solely to the preparation of organosols containing an individual organic solvent, it should be understood that the invention is not limited to such sols, and that sols may also be prepared containing mixtures of organic solvents.

The term organic solvents" employed herein and in the appended claims is intended to refer to the type of solvents commonly employed in the field of coating compositions, such as varnishes, lacquers, and the like, and commonly understood by chemists as suitable for such purposes. The term is also intended to include, howv .7313 at 60 F. and the following A. S. T. M. distillation range:

Per cent Distilled Temperature F. Initial Boiling Point. 200 50% Distilled 220 90% Distiiled 240 This application is a division of my co-pending application Serial No. 409,434, filed September 3, 1941, now Patent No. 2,386,247, granted October 9, 1945, which is a continuation-in-part of application Serial No. 272,404, filed May 8, 1939, and granted June 9, 1942, as-Patent No. 2,285,449.

What I claim is:

l. The method of preparing a stable and substantially anhydrous organosol composed of a colloidal inorganic oxide and a high'boilinghydrocarbon solvent which comprises forming an aquasol containing a colloidal inorganic oxide and a dissolved inorganic salt, adding normal propyl alcohol in an amount suiilcient'to precipitate the inorganic salt and to permit substantially complete removal of the water in said aquasol by distillation, then removing the precipitated inorganic salt, removing substantially all of the water by distillation, adding benzen and additional propyl alcohol to the resulting sol and removing further traces of water and substantially all of the benzene by distillation, adding a high boiling hydrocarbon selected from the group consisting of toluene and petroleum oil fractions boiling between 200 and 240 F. to the resulting propyl alcohol sol and removing the propyl alcohol by distillation.

2. The method of preparing a stable and substantially anhydrous organosol composed of colloidal silica and toluene which comprises forming an aquasol containing colloidal silica and a dissolved inorganic salt, adding normal propyl alcohol in an amount suflicient to precipitat the inorganic salt and to permit substantially complete removal of the water in said aquasol by distillation, then removing the precipitated inorganic salt, removing substantially all of the water by distillation, adding additional propyl alcohol and benzene to the resulting sol and removing further traces of water and substantially all of the benzene by distillation, adding toluene to the resulting propyl alcohol sol and removing the propyl alcohol by distillation.

. MORRIS D.

REFERENCES CITED The following references are of record in the flle of this patent:

UNITED STATES PATENTS Number Name Date 2,375,738 White May 8, 1945 2,386,247 Marshall Oct. 9, 1945 

